Electroluminescence and electric current response spectroscopy applied to the characterization of polymer light-emitting electrochemical cells

Frequency-dependent electroluminescence and electric current response spectroscopy were applied to polymeric light-emitting electrochemical cells in order to obtain information about the operation mechanism regimes of such devices. Three clearly distinct frequency regimes could be identified: a dielectric regime at high frequencies; an ionic transport regime, characterized by ionic drift and electronic diffusion; and an electrolytic regime, characterized by electronic injection from the electrodes and electrochemical doping of the conjugated polymer. From the analysis of the results, it was possible to evaluate parameters like the diffusion speed of electronic charge carriers in the active layer and the voltage drop necessary for operation. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4752438]

Photo luminescent polymer electrolyte based on agar and containing europium picrate for electrochemical devices

Dispersion of photoluminescent rare earth metal complexes in polymer matrices is of great interest due to the possibility of avoiding the saturation of the photoluminescent signal. The possibility of using a natural ionic conducting polymer matrix was investigated in this study. Samples of agar-based electrolytes containing europium picrate were prepared and characterized by physical and chemical analyses. The FTIR spectra indicated strong interaction of agar O-H and 3.6-anhydro-galactose C-O groups with glycerol and europium picrate. The DSC analyses revealed no glass transition temperature of the samples in the -60 to 250 degrees C range. From the thermogravimetry (TG), a thermal stability of the samples of up to 180 degrees C was stated. The membranes were subjected to ionic conductivity measurement, which provided the values of 2.6 x 10(-6) S/cm for the samples with acetic acid and 1.6 x 10(-5) S/cm for the samples without acetic acid. Moreover, the temperature-dependent ionic conductivity measurements revealed both Arrhenius and VTF models of the conductivity depending on the sample. Surface visualization through scanning electron microscopy (SEM) demonstrated good uniformity. The samples were also applied in small electrochromic devices and showed good electrochemical stability. The present work confirmed that these materials may perform as satisfactory multifunctional component layers in the field of electrochemical devices. (C) 2012 Elsevier B.V. All rights reserved.

Electrochromic Properties of a Metallo-supramolecular Polymer Derived from Tetra(2-pyridyl-1,4-pyrazine) Ligands Integrated in Thin Multilayer Films

The electrochromic behavior of iron complexes derived from tetra-2-pyridyl-1,4-pyrazine (TPPZ) and a hexacyanoferrate species in polyelectrolytic multilayer adsorbed films is described for the first time. This complex macromolecule was deposited onto indium-tin oxide (ITO) substrates via self-assembly, and the morphology of the modified electrodes was studied using atomic force microscopy (AFM), which indicated that the hybrid film containing the polyelectrolyte multilayer and the iron complex was highly homogeneous and was approximately 50 nm thick. The modified electrodes exhibited excellent electrochromic behavior with both intense and persistent coloration as well as a chromatic contrast of approximately 70%. In addition, this system achieved high electrochromic efficiency (over 70 cm(2) C-1 at 630 nm) and a response time that could be measured in milliseconds. The electrode was cycled more than 10(3) times, indicating excellent stability.

Performance of a poly(2,5-benzimidazole)-based polymer electrolyte membrane fuel cell

The performance of an ABPBI-based High Temperature H-2/O-2 PEMFC system was studied under different experimental conditions. Increasing the temperature from 130 to 170 degrees C improved the cell performance, even though further increase was not beneficial for the system. Humidification of the H-2 stream ameliorated this behaviour, even though operating above 170 degrees C is not advisable in terms of cell performance. A significant electrolyte dehydration seems to negatively affect the fuel cell performance, especially in the case of the anode. In the presence of 2% vol. CO in the H-2 stream, the temperature exerted a positive effect on the cell performance, reducing the strong adsorption of this poison on the platinum sites. Moreover, humidification of the H-2 + CO stream increased the maximum power densities of the cell, further alleviating the CO poisoning effects. Actual CO-O-2 fuel cell results confirmed the significant beneficial effect of the relative humidity on the kinetics of the CO oxidation process. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Conductive polymer gas sensor for quantitative detection of methanol in Brazilian sugar-cane spirit

A low-cost chemiresistive gas sensor is described, made by the deposition of a thin film of a conductive polymer, poly(2-dodecanoylsulfanyl-p-phenylenevinylene), doped with dodecylbenzenesulfonic acid (10%, w/w), onto interdigitated electrodes. The sensor exhibits linear electrical conductance changes in function of the concentration of methanol present in sugar-cane spirit in the range between 0.05% and 4.0%. Since the sensor is cheap, easy to fabricate, durable, presents low power consumption, and is not sensitive to ethanol, acetic acid or water, it can be used in portable equipments for monitoring methanol levels in distilled alcoholic beverages such as Brazilian sugar-cane spirit (cachaca). (C) 2011 Elsevier Ltd. All rights reserved.

Novel polymer electrolytes based on gelatin and ionic liquids

This study describes the results of the characterization of polymer electrolytes using gelatin matrix doped with europium triflate and/or different ionic liquids. Samples of solvent-free electrolytes were prepared and characterized by ionic conductivity measurements, thermal analysis, electrochemical stability, X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence spectroscopy. Electrolyte samples are thermally stable up to approximately 220 degrees C. All the materials synthesized are totally amorphous. The room temperature conductivity maximum of this electrolyte system is based on ionic liquid 1-ethyl-3-methylimidazolium acetate, (C(2)mim)(OAc) (1.18 x 10(-4) S cm(-1) at 30 degrees C). The electrochemical stability domain of all samples is about 2.0 V versus Li/Li+. This new series of materials represents a promising alternative in polymer electrolytes research field. The preliminary studies carried out with electrochromic devices (ECDs) incorporating optimized compositions have confirmed that these materials may perform as satisfactory multifunctional component layers in the field of "smart windows". This new materials, will open a land of promising applications in many areas: optics, energy, medicine for example as membranes and separation devices, ECD-based devices, sensors, etc. (C) 2012 Elsevier B.V. All rights reserved.

Gellan Gum-LiI Gel Polymer Electrolytes

Gellan-based polymer electrolytes (PEs), doped with lithium iodide (LiI), were prepared and their electrical properties were characterized. The samples are thermally stable up to 234 degrees C and exhibit ionic conductivity of 3.8 x 10(-4) S/cm at room temperature for the sample doped with 40 wt% of LiI. Addition of 10 wt% of glycerol promotes an increase of the ionic conductivity to 1.5 x 10(-3) S/cm, which remains stable up to 100 degrees C. The activation energies of 2.4 to 12.4 kJ/mol were derived from the Arrhenius model. The repeated ionic conductivity measurements as a function of temperature show that these membranes can be reversibly used between the room temperature and 100 degrees C.

Triboelectricity: Macroscopic Charge Patterns Formed by Self-Arraying Ions on Polymer Surfaces

Tribocharged polymers display macroscopically patterned positive and negative domains, verifying the fractal geometry of electrostatic mosaics previously detected by electric probe microscopy. Excess charge on contacting polyethylene (PE) and polytetrafluoroethylene (PTFE) follows the triboelectric series but with one caveat: net charge is the arithmetic sum of patterned positive and negative charges, as opposed to the usual assumption of uniform but opposite signal charging on each surface. Extraction with n-hexane preferentially removes positive charges from PTFE, while 1,1-difluoroethane and ethanol largely remove both positive and negative charges. Using suitable analytical techniques (electron energy-loss spectral imaging, infrared microspectrophotometry and carbonization/colorimetry) and theoretical calculations, the positive species were identified as hydrocarbocations and the negative species were identified as fluorocarbanions. A comprehensive model is presented for PTFE tribocharging with PE: mechanochemical chain homolytic rupture is followed by electron transfer from hydrocarbon free radicals to the more electronegative fluorocarbon radicals. Polymer ions self-assemble according to Flory-Huggins theory, thus forming the experimentally observed macroscopic patterns. These results show that tribocharging can only be understood by considering the complex chemical events triggered by mechanical action, coupled to well-established physicochemical concepts. Patterned polymers can be cut and mounted to make macroscopic electrets and multipoles.

Flexural strengthening of reinforced concrete beams with carbon fibers reinforced polymer (CFRP) sheet bonded to a transition layer of high performance cement-based composite

Resistance to corrosion, high tensile strength, low weight, easiness and rapidity of application, are characteristics that have contributed to the spread of the strengthening technique characterized by bonding of carbon fibers reinforced polymer (CFRP). This research aimed to develop an innovate strengthening method for RC beams, based on a high performance cement-based composite of steel fibers (macro + microfibers) to be applied as a transition layer. The purpose of this transition layer is better control the cracking of concrete and detain or even avoid premature debonding of strengthening. A preliminary study in short beams molded with steel fibers and strengthened with CFRP sheet, was carried out where was verified that the conception of the transition layer is valid. Tests were developed to get a cement-based composite with adequate characteristics to constitute the layer transition. Results showed the possibility to develop a high performance material with a pseudo strain-hardening behavior, high strength and fracture toughness. The application of the strengthening on the transition layer surface had significantly to improve the performance levels of the strengthened beam. It summary, it was proven the efficiency of the new strengthening technique, and much information can be used as criteria of projects for repaired and strengthened structures.

Porous Polymeric Bioresorbable Scaffolds for Tissue Engineering

Tissue engineering is a discipline that aims at regenerating damaged biological tissues by using a cell-construct engineered in vitro made of cells grown into a porous 3D scaffold. The role of the scaffold is to guide cell growth and differentiation by acting as a bioresorbable temporary substrate that will be eventually replaced by new tissue produced by cells. As a matter or fact, the obtainment of a successful engineered tissue requires a multidisciplinary approach that must integrate the basic principles of biology, engineering and material science. The present Ph.D. thesis aimed at developing and characterizing innovative polymeric bioresorbable scaffolds made of hydrolysable polyesters. The potentialities of both commercial polyesters (i.e. poly-e-caprolactone, polylactide and some lactide copolymers) and of non-commercial polyesters (i.e. poly-w-pentadecalactone and some of its copolymers) were explored and discussed. Two techniques were employed to fabricate scaffolds: supercritical carbon dioxide (scCO2) foaming and electrospinning (ES). The former is a powerful technology that enables to produce 3D microporous foams by avoiding the use of solvents that can be toxic to mammalian cells. The scCO2 process, which is commonly applied to amorphous polymers, was successfully modified to foam a highly crystalline poly(w-pentadecalactone-co-e-caprolactone) copolymer and the effect of process parameters on scaffold morphology and thermo-mechanical properties was investigated. In the course of the present research activity, sub-micrometric fibrous non-woven meshes were produced using ES technology. Electrospun materials are considered highly promising scaffolds because they resemble the 3D organization of native extra cellular matrix. A careful control of process parameters allowed to fabricate defect-free fibres with diameters ranging from hundreds of nanometers to several microns, having either smooth or porous surface. Moreover, versatility of ES technology enabled to produce electrospun scaffolds from different polyesters as well as “composite” non-woven meshes by concomitantly electrospinning different fibres in terms of both fibre morphology and polymer material. The 3D-architecture of the electrospun scaffolds fabricated in this research was controlled in terms of mutual fibre orientation by properly modifying the instrumental apparatus. This aspect is particularly interesting since the micro/nano-architecture of the scaffold is known to affect cell behaviour. Since last generation scaffolds are expected to induce specific cell response, the present research activity also explored the possibility to produce electrospun scaffolds bioactive towards cells. Bio-functionalized substrates were obtained by loading polymer fibres with growth factors (i.e. biomolecules that elicit specific cell behaviour) and it was demonstrated that, despite the high voltages applied during electrospinning, the growth factor retains its biological activity once released from the fibres upon contact with cell culture medium. A second fuctionalization approach aiming, at a final stage, at controlling cell adhesion on electrospun scaffolds, consisted in covering fibre surface with highly hydrophilic polymer brushes of glycerol monomethacrylate synthesized by Atom Transfer Radical Polymerization. Future investigations are going to exploit the hydroxyl groups of the polymer brushes for functionalizing the fibre surface with desired biomolecules. Electrospun scaffolds were employed in cell culture experiments performed in collaboration with biochemical laboratories aimed at evaluating the biocompatibility of new electrospun polymers and at investigating the effect of fibre orientation on cell behaviour. Moreover, at a preliminary stage, electrospun scaffolds were also cultured with tumour mammalian cells for developing in vitro tumour models aimed at better understanding the role of natural ECM on tumour malignity in vivo.

Liquid crystal polymer brushes and their application as alignment layers in liquid crystal cells

Liquid Crystal Polymer Brushes and their Application as Alignment Layers in Liquid Crystal Cells Polymer brushes with liquid crystalline (LC) side chains were synthesized on planar glass substrates and their nematic textures were investigated. The LC polymers consist of an acrylate or a methacrylate main chain and a phenyl benzoate group as the mesogenic unit which is connected to the main chain via a flexible alkyl spacer composed of six CH2 units. The preparation of the LC polymer brushes was carried out according to the “grafting from” technique: polymerization is carried out from azo-initiators that have been previously self-assembled on the substrate. LC polymer brushes with a thickness from a few nm to 230 nm were synthesized by varying the monomer concentration and the polymerization time. The LC polymer brushes were thick enough to allow for direct observation of the nematic textures with a polarizing microscope. The LC polymer brushes grown on untreated glass substrates exhibited irregular textures (“polydomains”). The domain size is in the range of some micrometers and depends only weakly on the brush thickness. The investigations on the texture-temperature relationship of the LC brushes revealed that the brushes exhibit a surface memory effect, that is, the identical texture reappears after the LC brush sample has experienced a thermal isotropization or a solvent treatment, at which the nematic LC state has been completely destroyed. The surface memory effect is attributed to a strong anchoring of the orientation of the mesogenic units to heterogeneities at the substrate surface. The exact nature of the surface heterogeneities is unknown. The effect was observed for the LC brushes swollen with low molecular weight nematic molecules, as well. Rubbing the glass substrate with a piece of velvet cloth prior to the surface modification with the initiator and the brush growth gives rise to the formation of homogenous alignment of the mesogenic units in the LC polymer side chains. Monodomain textures were obtained for these LC brushes. The mechanism for the homogeneous alignment is based on the transfer of Nylon fibers during the rubbing process. A surfactant was mixed with the azo-initiator in modifying rubbed substrates for subsequent brush generation. Such brushes exhibited biaxial optical properties. Hybrid LC cells made from a substrate modified with biaxial brushes and a rubbed glass substrate show an orientation with a tilt angle of a = –15.6 . This work shows that LC brushes grown on rubbed surfaces fulfill the important criteria for alignment layers: the formation of macroscopic monodomains. First results indicate that by diluting the brush with molecules which are also covalently bound to the surface but induce a different orientation, a system is obtained in which the two conflicting alignment mechanisms can be used to generate a tilted alignment. In order to allow for an application of the alignment layers into a potential product, subsequent work should focus on the questions how easy and in which range the tilt angle can be controlled.

A molecular dynamics study of the influence of chain branching on the properties of polymer systems

Die vorliegende Arbeit beschäftigt sich mit dem Einfluß von Kettenverzweigungen unterschiedlicher Topologien auf die statischen Eigenschaften von Polymeren. Diese Untersuchungen werden mit Hilfe von Monte-Carlo- und Molekular-Dynamik-Simulationen durchgeführt.Zunächst werden einige theoretische Konzepte und Modelle eingeführt, welche die Beschreibung von Polymerketten auf mesoskopischen Längenskalen gestatten. Es werden wichtige Bestimmungsgrößen eingeführt und erläutert, welche zur quantitativen Charakterisierung von Verzweigungsstrukturen bei Polymeren geeignet sind. Es wird ebenso auf die verwendeten Optimierungstechniken eingegangen, die bei der Implementierung des Computerprogrammes Verwendung fanden. Untersucht werden neben linearen Polymerketten unterschiedliche Topolgien -Sternpolymere mit variabler Armzahl, Übergang von Sternpolymeren zu linearen Polymeren, Ketten mit variabler Zahl von Seitenketten, reguläre Dendrimere und hyperverzweigte Strukturen - in Abhängigkeit von der Lösungsmittelqualität. Es wird zunächst eine gründliche Analyse des verwendeten Simulationsmodells an sehr langen linearen Einzelketten vorgenommen. Die Skalierungseigenschaften der linearen Ketten werden untersucht in dem gesamten Lösungsmittelbereich vom guten Lösungsmittel bis hin zu weitgehend kollabierten Ketten im schlechten Lösungsmittel. Ein wichtiges Ergebnis dieser Arbeit ist die Bestätigung der Korrekturen zum Skalenverhalten des hydrodynamischen Radius Rh. Dieses Ergebnis war möglich aufgrund der großen gewählten Kettenlängen und der hohen Qualität der erhaltenen Daten in dieser Arbeit, insbesondere bei den linearen ketten, und es steht im Widerspruch zu vielen bisherigen Simulations-Studien und experimentellen Arbeiten. Diese Korrekturen zum Skalenverhalten wurden nicht nur für die linearen Ketten, sondern auch für Sternpolymere mit unterchiedlicher Armzahl gezeigt. Für lineare Ketten wird der Einfluß von Polydispersität untersucht.Es wird gezeigt, daß eine eindeutige Abbildung von Längenskalen zwischen Simulationsmodell und Experiment nicht möglich ist, da die zu diesem Zweck verwendete dimensionslose Größe eine zu schwache Abhängigkeit von der Polymerisation der Ketten besitzt. Ein Vergleich von Simulationsdaten mit industriellem Low-Density-Polyäthylen(LDPE) zeigt, daß LDPE in Form von stark verzweigten Ketten vorliegt.Für reguläre Dendrimere konnte ein hochgradiges Zurückfalten der Arme in die innere Kernregion nachgewiesen werden.

Fourier-transform rheology on anionically synthesised polymer melts and solutions of various topology

Aim of this thesis was to further extend the applicability of the Fourier-transform (FT) rheology technique especially for non-linear mechanical characterisation of polymeric materials on the one hand and to investigated the influence of the degree of branching on the linear and non-linear relaxation behaviour of polymeric materials on the other hand. The latter was achieved by employing in particular FT-rheology and other rheological techniques to variously branched polymer melts and solutions. For these purposes, narrowly distributed linear and star-shaped polystyrene and polybutadiene homo-polymers with varying molecular weights were anionically synthesised using both high-vacuum and inert atmosphere techniques. Furthermore, differently entangled solutions of linear and star-shaped polystyrenes in di-sec-octyl phthalate (DOP) were prepared. The several linear polystyrene solutions were measured under large amplitude oscillatory shear (LAOS) conditions and the non-linear torque response was analysed in the Fourier space. Experimental results were compared with numerical predictions performed by Dr. B. Debbaut using a multi-mode differential viscoelastic fluid model obeying the Giesekus constitutive equation. Apart from the analysis of the relative intensities of the harmonics, a detailed examination of the phase information content was developed. Further on, FT-rheology allowed to distinguish polystyrene melts and solutions due to their different topologies where other rheological measurements failed. Significant differences occurred under LAOS conditions as particularly reflected in the phase difference of the third harmonic, Ħ3, which could be related to shear thinning and shear thickening behaviour.